1-methyl-2-hydroxy-4-aminobenzene as a modifier for oxidation dyes



United States Patent The present invention relates to a method and composition for the dyeing of hair and the like, particularly human hair.

Fast dyeing of hair keratin with certain soluble, initially colorless, dye intermediates which are adapted to be oxidized into colored dyes, either by application of suitable oxidizing agents or in contact with the oxygen of the air, has been proposed long ago. This method was first used for the dyeing of furs. However, when it was at- "ice dyed 1-methyl-2-hydroxy-4-aminobenzene, a substance selected from the group consisting of aromatic p-diamines and p-aminophenols, and an oxidizing agent.

Surprisingly, it has been found according to the present invention that oxidative dyeing of keratin-containing material, can be carried out so as to obtain brilliant colors of high stability, by applying to the material which is to be dyed, such as living hair, a mixture of one or more aromatic p-diamines and/or one or more p-aminophenols, together with 1-methy1-2-hydroxy-4-aminobenzene.

Very clear and pure color shades are obtained by applying equimolar amounts of a .p-aminophenol or aromatic p-diamine and of 1-methyl-2-hydroxy-4-aminobenzene.

The above described mixture may be applied as an aqueous or alcoholic solution, or dispersed in other suittempted to dye living human hair in this manner, serious 1 ditficulties were encountered due to the fact that the requirements in connection with dyeing living human hair are, of course, much more strict than those pertaining to the dyeing of furs or cut, dead hair. Thus, the compositions used for dyeing living hair should be non-toxic and should not cause allergies. Furthermore, the dyed living hair should maintain its color even when subjected to sunlight, moisture, acidic sweat, hair washing compositions and other chemicals used in the care of living hair, for instance hair waving and fixing preparations. It is desired that the developed hair dye on the living hair should be resistant against the above mentioned and other influences so that the desired and initially obtained color will be maintained.

In addition, the color obtained by dyeing hair with a given composition should be the same regardless of the color of the undyed hair.

- In view of the many requirements made with respect to dyeing compositions which are to be applied to the living hair, it has not been possible up to now to provide hair dyeing methods and compositions suitable for dyeing hair in every desired color and shade, and particularly not for dyeing living hair in certain fashionable shades which differ from natural hair colors.

It is therefore an object of the present invention to overcome the above mentioned difficulties with respect to the dyeing of hair in certain colors.

It is another object of the present invention to provide a hair dyeing composition and method which can be applied to living hair and will result in giving to the same a desired color of high resistance against chemical and physical attack.

It is yet another object of the present invention to dye hair, including living hair, in brilliant color shades, such as gold, red, mahogany and bordeaux, in a simple and effective manner.

The dyeing of hair according to the present invention may serve the purpose of giving to the hair the thus obtained color, or to shade thereby the hair color obtained by means of other hair dyeing compositions.

able carrier substances, so that the dyeing composition may be applied in any desired consistency, preferably in liquid or cream-like consistency.

The dyeing composition may be adjusted so as to react slightly alkaline, neutral or slightly acidic, broadly within a pH range from 2 to 11. In many cases it is particularly advantageous and will result in colors of greater lumi-.

nosity, to adjust the dyeing composition with ammonia to a slightly alkaline pH.

It is essential according to the present invention that the dyeing composition contains 1-methyl-2-hydroxy-4-aminobenzene. In combination therewith any aromatic pdiamine or p-aminophenol may be used.

Good results were obtained by incorporating in the dyeing composition of the present invention the following p-diamines or p-aminophenols:

1,4-diaminobenzene 1,2,4-triaminobenzene 1-methyl-2,5-diaminobenzene l,4-dimethyl-2,5 diaminobenzene l-methoxy-4-chloro-2,S-diaminobenzene 1-methoxy-4-methyl-2,S-diaminobenzene 1-amino-4-hydroxy-benzene 1-amino-2-methyl-4-hydroxy-benzene 1-amino-3 -m ethyl-4-hydroxy-benzene l,3-diamino-4-hydroxy-benzene 4,4-diaminodiphenylamine It is also within the scope of the present invention to incorporate in the dyeing composition detergents such as Other objects and advantages of the present invention fatty alcohol sulfonates, alkyl-aryl sulfonates, condensates of fatty alcohol-polyethylene oxide or fatty acid-methyltaurine condensation products; or thickening agents such as polyvinyl alcohol, polyacrylic acid ester, methylcellulose and carboxymethylcellulose such as is known under the trade name Tylose, or salts of alginic acid.

Suitable alcohols for forming an alcoholic or aqueous alcoholic solution of the essential components of the dyeing composition include ethanol, isopropanol and polyglycols.

Other additives which may be included in the dyeing composition of the present invention comprise perfume oils, certain essential oils and the like.

The following examples are given as illustrative only of the present invention without, however, limiting the invention to the specific details of the examples.

Example I A solution is formed of:

. Grams 1-methyl-2,5-diaminobenzene-sulfate 0.44 1-methyl-2-hydroxy-4-aminobenzene 0.25 Aqueous 25% ammonia solution 3.50 Distilled Water 95.81

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide and applied to the hair for between 20 and 30 minutes at body temperature- Thereafter, the hair is rinsed to remove the excess of the dyeing solution. In this manner a deep violet hair. color is obtained.

By neutralizing or acidifying the dyeing solution with acetic acid a brighter more shining hair color of slightly more reddish appearance is obtained.

Example [I A solution is formed of:

Grams 4,4-diaminodiphenylamineesulfate 0.594 1-methyl-2-hydroxy-4-aminobenzene 0.250 Aqueous 25% ammonia solution 3.500

Distilled water 95.656

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated with the thus formed mixture as described in Example I. A deep blue-violet hair color is obtained.

Example 111 A solution is formed of:

V Grams l-aminol-hydroxybenzene 0.218 1-methyl-2-hydroxy-4-aminobenzene 0.25 Aqueous 25 ammonia solution 3 .500

Distilled Water 96.032

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated With the thus formed mixture as described in Example I. A deep, full orange hair color is obtained.

Example IV A solution is formed of:

Grams 1-methyl-2,S-diaminobenzene-sulfate 0.440 1-amino-4-hydroxybenzene 0.218 1-methyl-2-hydroxy-4-aminobenzene 0.500 Aqueous 25 ammonia solution 7.000

Distilled Water 91.842

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated with the thus formed mixture as described in Example I. A deep red-violet hair color is obtained.

Example V A solution is formed of:

Grams 1-methyl-2,S-diaminobenzene-sulfate 0.220 1-amino-4-l1ydroxybenzene 0.218 1-methyl-2-hydroxy-4-aminobenzene 0.375 Aqueous 25% ammonia solution 5.000 Distilled Water 94.187

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated with the thus formed mixture as described in Example I. In this manner, beautiful ruby-colored hair is obtained.

Example VI A solution is formed of:

Grams 1,2,4-triaminobenzene-hydrochloride 0.392 l-methyl-2-hydroxy-4-aminobenzene 0.250 Aqueous 25% ammonia solution 3.500 Isopropanol 20.000 Distilled water 75.858

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated with the thus formed mixture as described in Example I. A bluish-black hair color is obtained.

4 Example VI] A solution is formed of:

Grams l-methyl-2,5-diaminobenzene 0.244 1-methyl-'2-hydroxy-4-aminobenzene 0.25 0

Distilled Water 99.506

Acetic acid is added so as to adjust the pH of the solution to 5.

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated with the thus formed mixture as described in Example I. A dark chestnut brown hair color is obtained.

Example VIII A solution is formed of:

Grams 1-methyl-2,S-diaminobenzene V 0.244 1-methyl-2-hydroxy-4-aminobenzene 0.25 0

Distilled water 99.506

The solution is adjusted to pH 7 (for adjusting the pH of the dyeing solutions, preferably either acetic acid or ammonia solution is used).

The thus formed solution is mixed with an equal volume of 6% aqueous hydrogen peroxide, and living hair is treated With the thus formed mixture as described in Example I. A dark mahogany hair color is obtained.

Example IX 20 grams 12% potassium oleate solution in 30 grams distilled water, are stirred into 15 grams molten fatty alcohol.

A smooth cream is obtained. A solution of the composition described below is stirred into the thus obtained cream:

Grams 1,4-dimethyl-2,S-diaminobenzene 0.272 1-rnethyl 2-hydroxy-4-aminobenzene 0.25 0

Distilled water 30.000 Aqueous 25% ammonia solution 3.500

In this manner an emulsion is obtained to which water is added up to a total weight of grams. The thus obtained emulsion of creamy consistency is then mixed with an equal volume of a 6% aqueous hydrogen peroxide solution and the thus obtained mixture applied to the hair. Application for a period of between 20 and 30 minutes will result in a deep blue-violet color of the thus dyed hair.

Example X A solution is formed of:

Grams- 1-amino-3-methyl-4-hydroxy-benzene 0.318 l-methyl-2-oxy-4-amino-benzene 0.250 Aqueous 25 ammonia solution 3.500 Fatty alcohol sulfonate 10.000 Distilled water 85.732

teristics of the generic or specific aspects of this inven tion and, therefore, such adaptations should and are in tended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Letters Patent is:

1. A method of dyeing hair, comprising the step of applying to hair which is to be dyed 1-methyl-2-hydroxy- 4-aminobenzene, at least one substance selected from the group consisting of 1-methyl-2,S-diaminobenzene, 1,4-diaminobenzene, 1,2,4-triaminobenzene, 1-methyl-2,5-diaminobenzene, 1,4-dimethyl-2,S-diaminobenzene, l-methoxy-4-chloro-2,5-diaminobenzene, 1-methoxy-4-methyl- 2,5-diaminobenzene, l-amino 4 hydroxy benzene, 1 amino-2-methyl-4-hydroxy-benzene, 1-amino-3-methyl-4- hydroxy-benzene, 1,3-diamino-4-hydroxy-benzene and 4,4-diaminodiphenylamine, and an effective amount of an oxidizing agent therefor.

2. A method of dying hair, comprising the step of applying to hair which is to be dyed substantially equimolar quantities of 1-methy1-2-hydroxy-4-aminobenzene, and of at least one substance selected from the group consisting of 1-methyl-2,5-diaminobenzene, 1,4-diaminobenzene, 1,2,4-triaminobenzene, 1-methyl-2,5-diamino benzene, 1,4-dimethyl-2,S-diaminobenzene, 1-methoxy-4- chlor0-2,5-diaminobenzene, 1-methoxy-4-methyl-2,5-di aminobenzene, 1-amino-4-hydroxy-benzene, 1-amino-2- methyl-4-hydroxy-benzene, 1-amino-3-methyl-4-hydroxybenzene, 1,3-diamino-4-hydroxy-benzene, and 4,4-diaminodiphenylamine, and an effective amount of hydrogen peroxide as an oxidizing agent therefor.

3. A method of dyeing hair, comprising the step of applying to hair which is to be dyed 1-methyl-2-hydroxy- 4-aminobenzene, at least one aromatic p-diamine adapted to form a hair dye upon oxidation, and an effective amount of oxidizing agent therefor.

4. A method of dyeing hair, comprising the step of applying to hair which is to be dyed I-methyl-Z-hydroxy- 44aminobenzene, :at least one p-aminop'henol adapted to form a hair dye upon oxidation, and an effective amount of oxidizing agent therefor.

5. A method of dyeing hair, comprising the step of applying to hair which is to be dyed a carrier substance compatible With hair and having distributed therethrough substantially equimolar quantities of 1 methyl 2 hydroxy- 4 aminobenzene, and of at least one substance selected from the group consisting of 1 methyl 2,5 diaminobenzene, 1,4 diaminobenzene, 1,2,4 triaminobenzene, 1 methyl 2,5 diaminobenzene, 1,4 dimethyl 2,5- diaminobenzene, 1 methoxy 4 chloro 2,5 diaminobenzene, 1 methoxy 4 methyl 2,5 diaminobenzene, 1 amino 4 hydroxy benzene, 1 amino 2 methyl- 4 hydroxy benzene, 1 amino 3 methyl 4 hydroxy benzene, 1,3 diamino 4 hydroxy benzene and 4,4-diaminodiphenylamine, and an effective amount of hydrogen peroxide as an oxidizing agent therefor.

6. A composition of matter for dyeing of hair which comprises 1 methyl 2 hydroxy 4 aminobenzene, at least one substance selected from the group consisting of 1 methyl 2,5 diaminobenzene, 1,4 diaminobenzene, 1,2,4 triaminobenzene, 1 methyl -2,5 diaminobenzene, 1,4 dimethyl 2,5 diaminobenzene, 1 methoxy 4- chloro 2,5 diaminobenzene, 1 methoxy- 4 methyl- 2, 5 diaminobenzene, 1 amino 4 hydroxy benzene, 1 amino 2 methyl 4 hydroxy benzene, 1 amino- 3 methyl 4 hydroxy benzene, 1,3 diamino 4- hydroxy benzene, and 4,4 diaminodiphenylamine, and an effective amount of an oxidizing agent therefor.

7. A composition of matter for dyeing of hair Which comprises substantially equimolar quantities of 1 methyl- 2 hydroxy 4 aminobenzene and of at least one substance selected from the group consisting of 1 methyl- 2,5 diaminobenzene, 1,4 diaminobenzene, 1,2,4 triaminobenzene, 1 methyl 2,5 diaminobenzene, 1,4- dimethyl 2,5 diaminobenzene, 1 methoxy 4 chloro- 2,5 diaminobenzene, 1 methoxy 4 methyl 2,5 diamino benzene, 1 amino 4 hydroxy benzene, 1- amino 2 methyl 4 hydroxy benzene, 1 amino 3- methyl 4 hydroxy benzene, 1,3 diamino 4 hydroxy benzene, and 4,4-diaminodiphenylamine, and an eifective amount of hydrogen peroxide as an oxidizing agent therefor.

8. A composition of matter for dyeing of hair which comprises 1-methyl-2-hydroxy-4-aminobenzene, at least one aromatic p-diamine adapted to form a hair dye upon oxidation, and an effective amount of an oxidizing agent therefor.

9. A composition of matter for dyeing of hair which comprises 1-methyl-2-hydroxy-4-aminobenzene, at least one p-aminophenol adapted to form a hair dye upon oxidation, and an effective amount of an oxidizing agent therefor.

10. A composition of matter for dyeing of hair which comprises a carrier substance compatible With hair and having distributed therethrough substantially equimolar quantities of 1-methyl-2-hydroxy-4-aminobenzene and of at least one substance selected from the group consisting of 1-methyl-2,S-diaminobenzene, 1,4-diaminobenzene, 1, 2,4 triaminobenzene, 1 methyl 2,5 diaminobenzene, 1,4-dimethyl 2,5 diaminobenzene, 1 methoxy 4- chloro 2,5 diaminobenzene, 1 methoxy 4 methyl- 2, 5 diaminobenzene, 1 amino 4 hydroxy benzene, 1 amino 2 methyl 4 hydroxy benzene, 1 amino- 3 methyl 4 hydroxy benzene, 1,3 diamino 4 hydroxy-benzene and 4,4-diaminodiphenylamine, and an effective amount of hydrogen peroxide as an oxidizing agent therefor.

References Cited by the Examiner FOREIGN PATENTS 12/58 Great Britain.

OTHER REFERENCES JULIAN S. LEVlTT, Primary Examiner, 

1. A METHOD OF DYEING HAIR, COMPRISING THE STEP OF APPLYING TO HAIR WHICH IS TO BE DYED 1-METHYL-2-HYDROXY4-AMINOBENZENE, AT LEAST ONE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF 1-METHYL-2,5-DIAMINOBENZENE, 1,4-DIAMINOBENZENE, 1,2,4-TRIAMINOBENZENE, 1-METHYL-2,4-DIAMINOBENZENE, 1,4-DIMETHYL-2,5-DIAMINOBENZENE, 1-METHOXY-4-CHLORO-2,5-DIAMINOBENZENE, 1-METHOXY-4-METHYL2,5-DIAMINOBENZENE, 1-AMINO-4-HYDROXY-BENZENE, 1AMINO-2-METHYL-4-HYDROXY-BEZENE, 1-AMINO-3-METHYL-4HYDROXY-BENZENE, 1,3-DIAMINO-4-HYDROXY-BENZENE AND 4,4''-DIAMINODIPHENYLAMINE AND AN EFFECTIVE AMOUNT OF AN OXIDIZING AGENT THEREFOR. 